A Convenient Approach for Synthesis of (Z)-3-Butylidenephthalide Derivatives

Abstract

The reaction of n-Bul, i with phthalic anhydride derivatives leads to (Z)-3-butylidenephthalide derivatives.

Notes

1a: an yellowish oil (lit^3a,b: oil). R_f 0.70 (acetone:pet.ether-1:3). IR:3071, 1778, 1688. ¹HNMR(δ, ppm) 0.99(3H, t, J=7,3Hz, 11-H), 1.54(2H, sext, J=7.3Hz, 10-H), 2.46(2H, dt, J=7.8, 7.3Hz, 9-H), 5.65(1H, t, J=7.8Hz, 8-H), 7.4–7.9(4H, m, Ar-H). m/z(FAB): 189([M+1], 100%), 159(43). 1b: colorless needles. m.p.: 149–151°C (lit^le: 150–153°C). R_f 0.35(acetone:pet.ether=1:3). IR: 3235(OH), 1740(C=O), 1651, 1605. ¹HNMR(δ, ppm): 0.97(3H, t, J=7.3Hz, 11-H), 1.59(2H, sext, J=7.3Hz, 10-H), 2.45(2H, m, 9-H), 5.99(1H, t, J=7.8Hz, 8-H), 7.02(1H, dd, J=7.8, 1.OHz, 5-H), 7.33 (1H, t, J=7.8Hz, 6-H), 7.50(1H, dd, J=7.8, 1.OHz, 7-H). m/z(EI): 204(M¹, 43%), 175(100), 162(15), 147(45). 1c: white solid. m.p: 97–100°C(lit^lc: 95–100°C). R_f 0.30(acetone:pt.ether=1:3). IR: 3243(OH). 1737(C=O), 1683, 1608. 1593. ¹HNMR(δ, ppm): 0.96(3H, t, J=7.1Hz, 11-H), 1.52(2H, sext, J=7.1Hz, 10-H), 2.40(2H, dt, J=7.7, 7.1Hz, 9-H), 5.60(1H, t, J=7.7Hz, 8-H), 7.00–7.10(2H, m, Ar-H), 7.85(1H, d, J=8.5Hz, Ar-H). m/z(El): 204(M⁺, 30%), 175(100), 162(68), 147(27). 1d: white solid. m.p.: 88–89°C(lit^3c: 85–87°C). R_f 0.43 (acetone: pet.ether=1:2). IR: 1774(C=O), 1680, 1611. ¹HNMR(δ, ppm): 1.03(3H, t, J=7.3Hz. 11-H), 1.56(2H, sext, J=7.3Hz, 10-H), 2.46(2H, dt, J=7.9, 7.3Hz, 9-H), 3.98(3H, s, OCH₃) 4.00(3H, s, OCH₃), 5.98(1H, t, J=7.9Hz, 8-H), 7.04(1H, d. J=8.0Hz, 6-H), 7.53(1H d, J=8.0, 7-H). m/z(EI): 248(M¹, 27%), 219(100), 206(15). 1e: white solid. m.p.: 109–112°C. R_f 0.36 (acetone:pet.ether=1:3). IR: 3310(OH), 1743(C=O), 1686, 1616. ¹HNMR (δ, ppm): 0.99(3H, t, J=7.3Hz, 11-H), 1.50(2H, sext, J=7.3Hz, 10-H), 2.44(2H, dt, J=7.8, 7.3Hz, 9-H), 5.48(1H t, J=7.8Hz, 8-H), 7.15–7.55(3H, m, Ar-H). m/z(FAB): 205([M+1]⁺, 100%), 175(17). 1f: an oil (lit^3f: oil). R_f 0.94(3H, t, J=7.0Hz, 11-H), 1.26–1.53(4H, m, 2xCH₂), 1.75(4H, m, 2xCH₂), 2.35(4H, m, 4-H and 7-H), 5.111(1H, t, J=7.7Hz, 8-H). m/z(EI): 192(M¹, 35%), 163(75), 149(75), 108(30). 1g: an oil. R_f 0.39(acetone: pet.ether=1:5). IR: 3035, 1755(C=O), 1698, 1641. ¹HNMR(δ, ppm): 0.85(3H, t, J=7.0Hz, 11-H), 1.38(6H, m, 8-, 9-and 10-H), 2.85(4H, br, s, 4H and 7-H), 4.75(1H, t, J=7.2Hz, 3-H), 5.75(2H, br. s, 5-H and 6-H). m/z(EI): 192(M¹, 44%), 163(7), 135(14), 107(100). 6: an colorless oil(lit^3f:oil). R_f 0.40(acetone: pet.ether=1:3). IR: 3360(OH), 1738(C=O). 1678.¹HNMR(δ, ppm): 0.83 (3H, t, J=7.0Hz, 11-H), 1.25(4H, m, 2xCH₂), 1.73(6H, m, 3xCH₂), 2.18(4H, m, 2xCH₂), 3.95(1H. br. s, OH, D₂O exchangeable). m/z(EI): 210(M⁺, 4%), 192(14), 153(100), 8: an yellowish oil. R_f 0.26(acetone:pet. ether=1:5). IR: 3400–2400(COOH), 1705(C=O), 1705(C=O), 1657. ¹HNMR(δ, ppm): 0.85(3H, br, s, CH₃), 1.3(4H, m, 2xCH₂), 2.4(6H, br, s, 3xCH₂), 2.9(2H, br, s, 2xCH), 5.6(2H, br, s, 2x equeals;CH), 11.1(1H, br, s, COOH). m/z(EI): 210(M⁺, 4%), 192(32), 164(14), 122(12), 107(31), 79(100).